Herbicidal compositions and methods employing esters of N-phosphonomethylglycine

ABSTRACT

N-phosphonomethylglycine and novel derivatives thereof useful as phytotoxicants or herbicides.

This is a division of Ser. No. 170,385, filed Aug. 9, 1971, now U.S.Pat. No. 3,799,758 which was a continuation-in-part of application Ser.No. 123,057, filed Mar. 10, 1971, now abandonded.

This invention relates to novel N-phosphonomethylglycines which areuseful as herbicides or phytotoxicants. This invention further relatesto phytotoxicant compositions and to herbicidal methods.

The term "phytotoxicant" as used herein means materials which (1)effectively control all plants in a given locus or (2) selectivelycontrol the growth of one or more plant species in the presence of otherplants. In like manner, "phytotoxic" and "phytotoxicity" are used toidentify the overall and selective control activity of the compounds andcompositions of this invention. The term "control" as used herein isinclusive of the actions of (1) killing, (2) inhibiting growth,reproduction or proliferation, and (3) removing, destroying or otherwisediminishing the occurrence and activity of plants and is applicable toany of the stated actions, or any combination thereof.

The term "plant" as used herein means terrestrial plants and aquaticplants.

The term "terrestrial plant" is inclusive of germinating seeds, emergingseedlings and herbaceous vegetation including the roots and above-groundportions, as well as established woody plants.

The term "aquatic plant" means algae and higher aquatic plants. The term"higher aquatic plant" means aquatic plants which are botanically higherthan algae and is inclusive of vegetative organisms growing in water inwhich a major part of such organisms are normally largely submerged,e.g. roots as in Lemna, leaves as in Vallisneria or entire plants suchas Anacharis. Thus, the term "higher aquatic plant" is inclusive of allwater plants whether normally free-floating in their environing watersuch as Salvinia, or immersed species which are normally rooted in soilsuch as Vallisneria, as well as species which appear to grow normally inall respects either free-floating or rooted such as Anacharis orAlternanthera.

The N-phosphonomethylglycines of this invention are ##STR1## wherein R,R¹ and R² are independently selected from the group consisting of:

HALOGEN; --OH; --SH;

--NR⁴ R⁵ wherein R⁴ and R⁵ are independently selected from the groupconsisting of hydrogen, alkyl and hydroxyalkyl having 1 through 4 atoms,alkenyl having 2 through 4 carbon atoms, and R⁴ and R⁵ together with thenitrogen atom can form a heterocyclic ring;

--OR³ and --SR³ wherein R³ is selected from the group consisting ofmonovalent hydrocarbon groups, monovalent hydrocarbonoxyhydrocarbongroups each containing from 1 to 18 carbon atoms, halogenated monovalenthydrocarbon groups, halogenated monovalent hydrocarbonoxyhydrocarbongroups each containing from 1 to 18 carbon atoms and from 1 to 3halogens, ##STR2## groups wherein n is from 1 to 4 and R⁴ and R⁵ are asabove defined provided that no more than two of R, R¹ or R² can be --NR⁴R⁵, -- OR³ or --SR³ ; and

--OR⁶ wherein R⁶ is a salt-forming cation selected from the groupconsisting of cations of alkali metals, alkaline earth metals, copper,zinc, manganese, nickel, ammonium, organic ammonium, provided that whenthe organic group is aryl the ammonium salt is a primary amine salt, andmixtures of such salts, provided that when any one of R, R¹ or R² ishalogen the others of R, R¹ or R² cannot be --OR⁶, and further providedthat no more than two of R, R¹ or R² are --OR⁶ when R⁶ is ammonium ororganic ammonium; and

the strong acid salts of said compounds of the formula where R, R¹ andR² are --OH, said strong acid having a pK of 2.5 or less.

The term halogen as employed herein means chlorine, bromine, iodine andfluorine.

The term monovalent hydrocarbon as used herein includes alkyl, alkenyl,alkynyl, aralkyl inclusive of both straight and branched chain radicals,such as methyl, ethyl, isopropyl, cyclopropyl, cyclohexyl, tertiarybutyl, n-butyl and the various forms of amyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, benzyl, phenylethyl, naphthylethyl,tolylethyl, methylbenzyl, phenylbenzyl, and the corresponding alkenyl,and alkynyl groups and the like, aryl groups and alkaryl groups such asphenyl, tolyl, xylyl, naphthyl, vinylphenyl and the like. It ispreferred that such monovalent hydrocarbon group contains from 1 to 18carbon atoms and be alkyl, alkenyl, or alkynyl groups.

The monovalent hydrocarbonoxyhydrocarbon groups represented by R³include alkoxyalkyl, alkenoxyalkyl, alkoxyalkoxyalkyl,alkenoxyalkoxyalkyl, dialkoxyalkyl, alkenoxy(alkoxy)alkyl,alkenoxyalkoxy(alkoxy)alkyl, alkoxyalkoxy(alkoxy)alkyl, aryloxyalkyl andalkoxyaryl such as 2-methoxyethyl, 4-ethoxy-2-methyl-butyl,2-ethoxyethyl, 3-propoxypropyl, 4-methoxybutyl, 4-methoxy-2-ethylbutyl,4-butoxybutyl, 2-allyloxyethyl, 2-butenoxyethyl, 4-butenoxybutyl,2-(2-methoxyethoxy)ethyl, 2-(2-butoxyethoxy)ethyl,4-(3-methoxypropoxy)butyl, 2-(3-allyloxypropoxy)ethyl,2-(2-butenoxyethoxy)ethyl, phenoxyethyl, naphthoxyethyl, butyl,2,4-diethoxyphenyl, 2-methoxyphenyl, tolyloxyethyl, 4-phenoxybutyl,trifluoromethylphenyl, and the like.

Illustrative of the halogenated monovalent hydrocarbon groupsrepresented by R³ are haloalkyl such as chloromethyl, iodomethyl,bromomethyl, fluoromethyl, chloroethyl, iodoethyl, bromoethyl,1,2-dichloroethyl, 1,2-diiodoethyl, 2,2-dibromoethyl, chloro-n-propyl,bromo-n-propyl, iodoisopropyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3-trichlorobutyl, 1,3,3 -tribromobutyl, chloropentyl, bromopentyl,2,3-dichloropentyl, 3,3-dibromopentyl, chlorohexyl, bromohexyl,2,4-dichlorohexyl, 1,3-dibromohexyl, 1,3,4-trichlorohexyl, chloroheptyl,bromoheptyl, fluoroheptyl, 1,3-dichloroheptyl, 1,4,4-trichloroheptyl,2,4-dichloromethylheptyl, chlorooctyl, bromooctyl, iodooctyl,2,4-dichloromethylhexyl, 2,4-dichlorooctyl, 2,4,4-trichloromethylpentyl,1,3,5-tribromooctyl and the halogenated straight and branched chainnonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl and octadecyl; haloalkenyl such as chlorovinyl,bromovinyl, chloroallyl, bromoallyl, 3-chloro-n-butenyl-1,3-chloro-n-pentenyl-1, 4-chloro-n-hexenyl-2,3,4-dichloromethylpentenyl-1, 3-fluoro-n-heptenyl-1,1,3,3-trichloro-n-heptenyl-5, 1,3,5-trichloro-n-octenyl-6,2,3,3-trichloromethylpentenyl-4 and the various homologues and isomersof haloalkenyl having 2 to 12 carbon atoms; haloaryl such aso-chlorophenyl, m-chlorophenyl, m-bromophenyl, p-chlorophenyl,2,4-dichlorophenyl, 3,5-dichlorophenyl, 2,5-diiodophenyl, and the like.The halogenated monovalent hydrocarbonoxyhydrocarbon groups representedby R³ are the alkoxy and aryloxy substituted derivatives of theforegoing halogenated monovalent hydrocarbon groups where the alkyl andaryl groups are those previously set forth.

The term "alkali-metal" encompasses lithium, sodium, potassium, cesiumand rubidium; and the term "alkaline earth metal" includes beryllium,magnesium, calcium, strontium and barium.

The organic ammonium salts of the above formula are those prepared fromlow molecular weight organic amines, i.e. having a molecular weightbelow about 300, and such organic amines include the alkyl amines,alkylene amines and alkanol amines containing not more than 2 aminegroups, such as methylamine, ethylamine, n-propylamine, isopropylamine,n-butylamine, isobutylamine, sec-butylamine, n-amylamine, iso-amylamine,hexylamine, heptylamine, octylamine, nonylamine, decylamine,undecylamine, dodecylamine, tridecylamine, tetradecylamine,pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine,methylethylamine, methylisopropylamine, methylhexylamine,methylnonylamine, methylpentadecylamine, methyloctadecylamine,ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine,hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-amylamine, diisoamylamine, dihexylamine,di-heptylamine, dioctylamine, trimethylamine, triethylamine,tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-secbutylamine, tri-n-amylamine, ethanolamine,n-propanolamine, isopropanolamine, diethanolamine,N,N-diethylethanolamine, N-ethylpropanolamine, N-butylethanolamine,allylamine, n-butenyl-2-amine, n-pentenyl-2-amine,2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine andpropylenediamine, primary aryl amines such as aniline, methoxyaniline,ethoxyaniline, o,m,p-toluidine, phenylenediamine, 2,4,6-tribromoaniline,benzidine, naphthylamine, o,m,p-chloroaniline, and the like; hetrocyclicamines such as pyridine, morpholine, piperidine, pyrrolidine, indoline,azepine and the like.

Among the preferred compounds of this invention are those of the aboveformula wherein at least one of R, R¹ and R² is OR³ or OR⁶ and theremaining members of R, R¹ and R² are OH, SH or OR⁶. The more preferredcompounds of this invention are those of the above formula wherein atleast one of R, R¹ and R² is OR⁶ and the remainder of R, R¹ and R² areOH, and wherein R⁶ is a salt-forming cation. The particularly preferredcompounds of this invention are those of the formula wherein one of R,R¹ and R² is OR⁶, the remaining ones are OH, and R⁶ is ammonium ororganic ammonium wherein the organic ammonium group is selected from thegroup consisting of monoalkylammonium, dialkylammonium,trialkylammonium, monoalkenylammonium, dialkenylammonium,trialkenylammonium, monoalkynylammonium, dialkynylammonium,trialkynylammonium, monoalkanolammonium, dialkanolammonium,trialkanolammonium, heterocyclic ammonium or an aryl ammonium, suchorganic ammonium group containing from 1 to 18 carbon atoms.

One compound encompassed by the above formula, namely,N-phosphonomethylglycine, is known. This is the compound identified bythe formula when each of R, R¹ and R² is --OH. The remainder of thecompounds in accordance with the generic formula are new. All of thecompounds of the present invention, however, are new and novelherbicides or phytotoxicants.

N-phosphonomethylglycine in itself is a very effective phytotoxicant orherbicide. Because it is relatively insoluble in water and conventionalorganic solvents, however, it is not as readily amenable to commercialformulation as are many of its derivatives. It is therefore generallypreferred to utilize the more readily soluble compounds of thisinvention in which at least one of the hydrogens in the hydroxy or thiolgroups of N-phosphonomethylglycine has been replaced with an alkalimetal or an alkaline earth metal or has been combined with ammonia or anorganic amine. The amino alkyl esters of N-phosphonomethylglycine arealso efficacious phytotoxicants. Surprisingly, these and other compoundsencompassed by the above general formula are water-soluble but yetexhibit the same high magnitude of activity as the glycine.

In addition, N-phosphonomethylglycine can be readily dehydrated to formlinear and cyclic anhydrides which are also excellent phytotoxicants orherbicides.

The N-phosphonomethylglycines can be prepared by thephosphonomethylation of a glycine, preferably withchloromethylphosphonic acids. They also can be prepared by the phosphiteaddition to azomethines. For example, the reaction of ethyl glycinatewith formaldehyde and diethylphosphite results in the formation of thetriethyl ester of N-phosphonomethylglycine. Also, the compounds underconsideration can be readily obtained by the oxidation of thecorresponding aminophosphinic compounds utilizing mercuric chloride andother oxidizing agents. The N-phosphonomethylglycines are granular orcrystalline solid materials generally soluble in water.

The strong acids which form salts with the N-phosphonomethylglycine arethose having a pK of 2.5 or less, for example, hydrochloric acid,sulfuric acid, phosphoric acid, trifluoroacetic, trichloroacetic and thelike. In some instances, these acid salts as isolated are the hemi-salt,i.e. one molecule of acid combines with 2 molecules of theN-phosphonomethylglycine and may contain water of hydration.

The acid halides of N-phosphonomethylglycine are prepared by knownmethods, for example chloro derivatives can be prepared by the reactionof N-phosphonomethylglycine with PCl₅ or SOCl₂ in an anhydrous solventmedium, such as an ether etc., or other organic solvent.

The amides, esters or thioesters of N-phosphonomethylglycine can beprepared by reacting the acid halide in a solvent with the appropriateamine, thiol, or alcohol in the presence of a hydrogen halide acceptorsuch as triethylamine, pyridine and the like; or by an ester interchangereaction with the methyl ester of N-phosphonomethylglycine.

The salts of N-phosphonomethylglycine are prepared by partial orcomplete neutralization of the acid with the appropriate base, basiccarbonate, ammonia or organic amine.

In accordance with this invention it has been found that the growth ofgerminating seeds, emerging seedlings, maturing and established woodyand herbaceous vegitation and aquatic plants can be controlled byexposing the emerging seedlings or above-ground portions of maturing andestablished vegetation, or the aquatic plants to the action of aneffective amount of the glycines of the present invention. The compoundscan be used individually, as admixtures of two or more compounds, or inadmixture with an adjuvant. These compounds are effective aspost-emergent phytotoxicants or herbicides, e.g., the selective controlof the growth of one or more monocotyledonous species and/or one or moredicotyledonous species in the presence of other monocotyledons and/ordicotyledones. Furthermore, these compounds are characterized by broadspectrum activity, i.e., they control the growth of a wide variety ofplants including but not limited to ferns, conifer (pine, fir and thelike), aquatic, monocotyledons and dicotyledons.

In the following examples, which illustrate the invention, andthroughout the specification, parts and percent are by weight unlessotherwise indicated.

EXAMPLE 1

A mixture of about 50 parts of glycine, 92 parts ofchloromethylphosphonic acid, 150 parts of 50% aqueous sodium hydroxideand 100 parts water was introduced into a suitable reaction vessel andmaintained at reflux temperature while an additional 50 parts of 50%aqueous sodium hydroxide was added. The pH of the reaction mixture wasmaintained between 10 and 12 by the rate of addition of the sodiumhydroxide. After all of the caustic solution had been added, thereaction mixture was refluxed for an additional 20 hours, cooled to roomtemperature and filtered. About 160 parts of concentrated hydrochloricacid were then added and the mixture filtered to provide a clearsolution which slowly deposited N-phosphonomethylglycine. This materialhad a melting point of 230°C with decomposition.

Calc'd. for C₃ H₈ NO₅ P: C, 21.31; H, 4.77; N, 8.28. Found: C, 21.02; H,5.02; N, 8.05.

EXAMPLE 2

N-phosphonomethylglycine was also prepared by the oxidation ofN-phosphinomethylglycine in accordance with the following method:

A mixture of about 107 parts of phosphinomethylglycine, 625 parts ofmercuric chloride and 50 parts of water were charged into a suitablereaction vessel and maintained at reflux temperature for about twohours. The mercurous chloride resulting from the reaction precipitatedout and was removed by filtration. The filtrate was saturated withhydrogen sulfide and the resultant mercuric sulfide removed therefrom byfiltration to provide a clear filtrate which was concentrated at reducedpressure and the residue diluted with 10 parts of water. The crystallineprpecipitate was collected and washed with methanol and then withdiethyl ether. The product thus obtained was identical to the product ofthe preceding example.

EXAMPLE 3

A mixture of about 17 parts of N-phosphonomethylglycine, 100 parts ofwater and 7 parts of potassium carbonate was agitated in a suitablereaction vessel at room temperature. After dissolution was complete asindicated by clarification of the reaction mixture, the reaction mixturewas concentrated on a steam bath at reduced pressure. The residue waswashed with hot methanol and then with diethyl ether. The product thusobtained is the monopotassium salt of N-phosphonomethylglycinehemihydrate.

Calc'd. for C₃ H₇ NO₅ PK. 1/2H₂ O: C, 16.65; H, 3.70; N, 6.46 Found: C,16.67; H, 3.85; N, 6.32

By increasing the amount of potassium carbonate used, the correspondingdipotassium and tripotassium salts of N-phosphonomethylglycine can beprepared. Corresponding ammonium salts and salts of other alkali metaland alkaline earth metal salts as well as copper, zinc, manganese andnickel salts are readily prepared in substantially the same manner.

Following the above procedure, the following salts ofN-phosphonomethylglycine were obtained as white powders:

Mono-, di-, and trisodium salts;

Mono-, di-, and trilithium salts.

EXAMPLE 4

About 170 parts of N-phosphonomethylglycine were added to a solution of45 parts of dimethylamine dissolved in 10 parts of water and containedin a suitable reaction vessel. The reaction mixture cleared within ashort period of time while the mixture was subject to agitation. Theresulting solution was then concentrated by heating to 100°C. at reducedpressure. The residue was a viscous oil from which a crystalline solidwas obtained. The product was identified as the mono-dimethylamine saltof N-phosphonomethylglycine, m.p. 150°C. with decomposition.

Calc'd. for C₅ H₁₅ N₂ O₅ P: C, 28.04; H, 7.06; N, 13.08; P, 14.66.Found: C, 27.88; H, 6.92; N, 12.88; P, 14.22.

Following the above procedure, other amine salts ofN-phosphonomethylglycine can be prepared, e.g., the pyridine salts(monosalt - white solid), the diethylamine salts, the morpholine salts,the piperidine salts, ethanol amine salt (deliquescent powder to viscousliquid), ammonium salt (white powder).

EXAMPLE 5

Gaseous hydrogen chloride was led through a suspension of 6 g. (0.0355mole) of N-phosphonomethylglycine in excess methyl alcohol until a clearsolution was obtained. The solution was concentrated at reduced pressureand the residue mixed with a solution of methanol containing at leastone equivalent of triethylamine. The solvent was removed at reducedpressure and the residue extracted with ether until granular. Thegranular solid was finally extracted with methanol to removetriethylamine hydrochloride. The insoluble product, methylN-phosphonomethylglycinate, was obtained in excellent yield. Afterrecrystallization from dilute methanol, the product melted withdecomposition at 208.5°C.

Calc'd. for C₄ H₁₀ NO₅ P: C, 26.24; H, 5.50. Found: C, 26.15; H, 5.43.

The following esters were prepared according to the above procedure (allmelt with decomposition at the temperature indicated):

    ______________________________________                                        dodecyl N-phosphonomethylglycinate                                                                     197-200°C.                                    chloroethyl N-phosphonomethylglycinate                                                                 207°C.                                        ethyl N-phosphonomethylglycinate                                                                       203°C.                                        cyclohexyl N-phosphonomethylglycinate                                                                  195°C.                                        decyl N-phosphonomethylglycinate                                                                       201-204°C.                                    hexyl N-phosphonomethylglycinate                                                                       202°C.                                        octyl N-phosphonomethylglycinate                                                                       200°C.                                        n-butyl N-phosphonomethylglycinate                                                                     207-209°C.                                    propyl N-phosphonomethylglycinate                                                                      208.5°C.                                      ______________________________________                                    

EXAMPLE 6

A mixture of 10 g. (0.055 mole) of methyl N-phosphonomethylglycinate andexcess concentrated aqueous ammonium hydroxide was heated at the refluxtemperature for two hours. The solution was then concentrated at reducedpressure, the residue washed with ether and methanol, and the granularproduct stirred with a mixture of excess glacial acetic acid inmethanol. The precipitated solid was collected, washed with methanol andcrystallized from dilute ethanol. The yield ofN-phosphonomethylglycinamide, m.p. 227°C. with decomposition; was 8 g.or 87% of the theoretical amount.

Calc'd. for C₃ H₉ N₂ O₄ P: C, 21.44; H, 5.40 Found: C, 21.26; H, 5.39

EXAMPLE 7

A solution of 16.9 g. (0.10 mole) of N-phosphonomethylglycine in 300mls. of hot water was heated at the reflux temperature with 5.6 g. (0.10mole) calcium oxide. After about ten minutes, the mixture was cooled andfiltered. The residue was washed with methanol and ether. Afterair-drying, the yield of calcium salt of N-phosphonomethylglycinehydrate was 17.5 g. or 84% of the theoretical yield.

Calc'd. for C₃ H₆ NO₅ PCa. 21/2 H₂ O: C, 13.73; H, 4.05; Ca, 15.76.Found: C, 13.75; H, 4.20; Ca, 15.28.

EXAMPLE 8

A mixture of 17 g. (0.10 mole) of N-phosphonomethylglycine and 2 g.(0.05 mole) of magnesium oxide in 300 mls. of water was heated at thereflux temperature for ten minutes. The solution was cooled to roomtemperature and filtered to remove a small amount of sediment. The clearfiltrate was then concentrated at reduced pressure and the granularresidue washed with methanol and ether. Magnesiumbis-N-phosphonomethylglycinate hydrate was obtained in excellent yield.

Calc'd. for C₆ H₁₄ N₂ O₁₀ P₂ Mg. 21/2 H₂ O: C, 17.79; H, 4.57; Mg, 5.56.Found: C, 17.80; H, 4.69; Mg, 6.00.

EXAMPLE 9

A mixture of 20 g. (0.11 mole) of methyl N-phosphonomethylglycinate andabout 23 g. (0.33 mole) of pyrrolidine was heated on a steam bath fortwo hours. Excess amine was then removed at reduced pressure and theresidue washed with ether and tetrahydrofuran. The gummy product wasstirred with a mixture of excess glacial acetic acid in methanol and thecrystalline precipitate collected by filtration. After washing withmethanol and ether, the tetramethylene N-phosphonomethylglycinamide,m.p. 243°C. with decomposition, was obtained in a yield of 12 g. or 49%of the theoretical amount. The product was recrystallized from diluteethanol for analysis.

Calc'd. for C₇ H₁₅ N₂ O₄ P: C, 37.84; H, 6.81 Found: C, 37.82; H, 6.96

EXAMPLE 10

N-phosphonomethylglycine (10 g.) was placed in a small beaker andcovered with concentrated hydrochloric acid (approximately 5 ml.). Afterthe exothermic reaction has subsided, the mixture was allowed to standabout 10 to 15 minutes. The crystalled solid was washed withtetrahydrofuran and then air-dried to yield an essentially quantitativeyield of N-phosphonomethylglycine hemihydrochloride hemihydrate (m.p.greater than 300°C.).

Other compounds of the present invention that can be made in generalaccordance with the foregoing procedure include:

N-chlorophosphonylmethylglycine

N-dichlorophosphonylmethylglycine

N-phosphonomethylglycinyl chloride

N-phosphonomethylglycinyl bromide

N-phosphonomethylglycinyl iodide

N-phosphonomethylglycinyl fluoride

N-dichlorophosphonylmethylglycinyl chloride

N-dibromophosphonylmethylglycine

N-diiodophosphonylmethylglycine

Monopyridine salt of N-phosphonomethylglycine

Monobutylamine salt of N-phosphonomethylglycine

Mono-(trimethylamine) salt of N-phosphonomethylglycine

Monopyrrolidine salt of N-phosphonomethylglycine

Mono(diethylenetriamine) salt of N-phosphonomethylglycine

Monoisopropylamine salt of N-phosphonomethylglycine

Mono-n-propylamine salt of N-phosphonomethylglycine

Monomorpholine salt of N-phosphonomethylglycine

Mono(dipropargylamine) salt of N-phosphonomethylglycine

Monosodium salt of ethyl N-phosphonomethylglycinate

Potassium salt of ethyl N-phosphonomethylglycinate

Mono(dialkylamine) salt of N-phosphonomethylglycine

Monolithium salt of ethyl-N-phosphonomethylglycinate

Monosodium salt of propyl-N-phosphonomethylglycinate

Monosodium salt of methyl-N-phosphonomethylglycinate

Monosodium salt of chloroethyl-N-phosphonomethylglycinate

Monosodium salt of hexyl-N-phosphonomethylglycinate

Monopotassium salt of methyl-N-phosphonomethylglycinate

Monopotassium salt of propyl-N-phosphonomethylglycinate

Monopotassium salt of butyl-N-phosphonomethylglycinate

Monopotassium salt of hexyl-N-phosphonomethylglycinate

Monopotassium salt of chloroethyl-N-phosphonomethylglycinate

Mono(picoline) salt of N-phosphonomethylglycine

Monocyclohexylamine salt of N-phosphonomethylglycine

Di(methylamine) salt of N-phosphonomethylglycine

Di(dimethylamine) salt of N-phosphonomethylglycine

Di(ethylamine) salt of N-phosphonomethylglycine

Di(n-propylamine) salt of N-phosphonomethylglycine

Di(iso-propylamine) salt of N-phosphonomethylglycine

Di(morpholine) salt of N-phosphonomethylglycine

Mono(oleylamine) salt of N-phosphonomethylglycine

Mono(steaylamine) salt of N-phosphonomethylglycine

Mono(tallowamine) salt of N-phosphonomethylglycine

Mono(methylbutylamine) salt of N-phosphonomethylglycine

N-difluorophosphonylmethylglycine

N-phosphonomethylglycine hemihydrobromide hemihydrate

N-phosphonomethyl thiolglycine

N-thiolphosphonomethylglycine

N-dithiolphosphonomethylglycine

chloropropyl-N-phosphonomethylglycine

N-trithiolphosphonomethylglycine

phenyl-N-phosphonomethylglycinate

naphthyl-N-phosphonomethylglycinate

methoxyethyl-N-phosphonomethylglycinate

dimethyl-N-(phosphonomethyl)glycinate

methyl-N-phosphonomethyl thiolglycine

decyl-N-phosphonomethyl thiolglycine

octadecyl-N-phosphonomethyl thiolglycine

N,n-dimethyl(N-phosphonomethyl)glycinamide

N,n-dibutyl(N-phosphonomethyl) glycinamide monosodium salt

N-(phosphonomethyl)glycine monoethylamine salt

dichloroethyl-N-(phosphonomethyl)glycinate

trichlorobutyl-N-(phosphonomethyl)glycinate

dibromohexyl-N-(phosphonomethyl)glycinate

trifluoromethylphenyl-N-(phosphonomethyl)glycinate

dichlorophenyl-N-(phosphonomethy)glycinate

dibutylamine salt of N-(phosphonomethyl)glycine

octadecylamine salt of N-(phosphonomethyl)glycine

methoxyethylamine salt of N-(phosphonomethyl) glycine

ethylenediamine salt of N-(phosphonomethyl)glycine

pyrrolidine salt of N-(phosphonomethyl)glycine

dipropanolamine salt of N-(phosphonomethyl)glycine

chloroethylamine salt of N-(phosphonomethyl)glycine

phenoxyethylamine salt of N-(phosphonomethyl)glycine

N,n-diethylaminoethyl-N-(phosphonomethyl)glycinate

EXAMPLE 11

In order to demonstrate the phytotoxic activity of the compounds of thisinvention against aquatic species, alligator weed (Alternantheraphiloperorides) was sprayed with an aqueous solution ofN-phosphonomethylglycine at the rate of 0.125 pound per acre. The plantswere maintained under greenhouse conditions for four weeks and theresponse of the plants was then noted. At the end of the four weekperiod, all of the plants were dead. Control plants were normal after 4weeks.

EXAMPLE 12

The post-emergence herbicidal activity of various compounds of thisinvention is demonstrated as follows. The active ingredients are appliedin spray form to 14 or 21 day old specimens (as indicated) of variousplant species. The spray, a water or organic solvent-water solutioncontaining active ingredient and a surfactant (35 parts butylamine saltof dodecylbenzenesulfonic acid and 65 parts tall oil condensed withethylene oxide in the ratio of 11 moles ethylene oxide to 1 mole talloil), is applied to the plants in different sets of pans at severalrates (pounds per acre) of active ingredient. The treated plants areplaced in a greenhouse and the effects are observed and recorded afterapproximately 2 weeks or approximately 4 weeks, as is indicated in thelast column of Table I.

The post-emergence herbicidal activity index used in Table I is asfollows:

    ______________________________________                                        PLANT RESPONSE                                                                             INDEX    PLANT RESPONSE                                                                              INDEX                                     ______________________________________                                        No injury    0        Severe injury 3                                         Slight injury                                                                              1        Killed        4                                         Moderate injury                                                                            2                                                                ______________________________________                                    

The plant species utilized in these tests are identified by letter inaccordance with the following legend:

    ______________________________________                                        A -- Soybean        K -- Smartweed                                            B -- Sugar Beet     L -- Velvetleaf                                           C -- Wheat          M -- Downy Brome                                          D -- Rice           N -- Panicum Spp                                          E -- Sorghum        O -- Barnyardgrass                                        F -- Cocklebur      P -- Crabgrass                                            G -- Wild Buckwheat Q -- Nutsedge*                                            H -- Morningglory   R -- Quackgrass*                                          I -- Hemp sesbania  S -- Johnsongrass*                                        J -- Lambsquarters  T -- Canada thistle*                                      ______________________________________                                         *Established from vegetive propagules.                                   

                                      TABLE I                                     __________________________________________________________________________    COMPOUND                                                                             RATE                                                                              A B C D E F G H I J K L M N O P Q R S T WEEKS                      __________________________________________________________________________    I      4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4 --                                                                              2 --                                                                              4 --                                                                              4 4 --                                                                              4 --                                                                              4 3 4 --                                                                              2                          I      1   0 1 3 1 3 2 1 2 0 2 --                                                                              1 3 4 3 3 --      --                                                                            --                                                                            --                                                                            4                          II     4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4 --                                                                              3 --                                                                              4 4 4 4 --                                                                              4 --                                                                              4       4                                                                             4                                                                             --                                                                            2                          II     1   3 4 4 3 4 3 2 3 3 4 --                                                                              4 4 4 4 4 --      --                                                            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                --                                                                            --                                                                            2                          VII    4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3 --                                                                              1 --                                                                              3 2 2 2 --                                                                              3 --                                                                              1       2                                                                             3                                                                             2                                                                             2                          VIII   4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3 --                                                                              2 --                                                                              3 $ 3 3 --                                                                              3 --                                                                              2       4                                                                             4                                                                             3                                                                             2                          IX     4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3 --                                                                              3 --                                                                              4 4 3 3 --                                                                              3 --                                                                              2       4                                                                             3                                                                             --                                                                            2                          X      4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              3 --                                                                              3 --                                                                              4 4 4 4 --                                                                              4 --                                                                              3       4                                                                             4                                                                             4                                                                             2                          XI     4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4 --                                                                              3 --                                                                              4 4 4 3 --                                                                              4 --                                                                              3    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                 4 --                                                                              4       4                                                                             --                                                                            4                                                                             2                          XXXI   4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4 --                                                                              4 --                                                                              4 --                                                                              4 4 --                                                                              4 --                                                                              4       4                                                                             --                                                                            4                                                                             2                          XXXII  4   --                                                                              --                                                                              --                                                                              --                                                                              --                                                                              4 --                                                                              4 --                                                                              4 --                                                                              4 4 --                                                                              4 --                                                                              4       4                                                                             --                                                                            4                                                                             2                          __________________________________________________________________________     *Applied to 3-week old plants. All other tests conducted on 2-week old        plants.                                                                       **These readings made after 11 days.                                     

The following are the compounds referred to by the Roman numerals in thetable:

    __________________________________________________________________________    ROMAN NUMERAL        COMPOUND NAME                                            __________________________________________________________________________    I          N-phosphonomethylglycine                                           II         Sodium N-phosphonomethylglycinate                                  III        Disodium N-phosphonomethylglycinate                                IV         Trisodium N-phosphonomethylglycinate                               V          N-Phosphonomethylglycine, mono-ethanolamine salt                   VI         N-Phosphonomethylglycine, mono-ammonium salt                       VII        Monohydrate calcium salt of N-phosphonomethylglycine               VIII       Magnesium salt of N-phosphonomethylglycine                         IX         Magnesium bis-(N-phosphonomethylglycinate)                         X          Potassium salt of N-phosphonomethylglycine                         XI         Dimethylamine salt of N-phosphonomethylglycine                     XII        Copper bis-(N-phosphonomethylglycinate)                            XIII       Dilithium salt of N-phosphonomethylglycine                         XIV        Zinc salt of N-(phosphonomethyl)glycine                            XV         N-Phosphonomethylglycinamide                                       XVI        Methyl-N-(phosphonomethyl)glycinate                                XVII       Ethyl-N-(phosphonomethyl)glycinate                                 XVIII      n-propyl-N-(phosphonomethyl)glycinate                              XIX        n-butyl-N-(phosphonomethyl)glycinate                               XX         n-hexyl-N-(phosphonomethyl)glycinate                               XXI        Cyclohexyl-N-(phosphonomethyl)glycinate                            XXII       Octyl-N-(phosphonomethyl)glycinate                                 XXIII      Decyl-N-(phosphonomethyl)glycinate                                 XXIV       Dodecyl-N-(phosphonomethyl)glycinate                               XXV        Chloroethyl-N-(phoshonomethyl)glycinate                            XXVI       Mono(methylamine) salt of N-phosphonomethylglycine                 XXVII      Mono(diisopropylamine) salt of N-phosphonomethyl-                             glycine                                                            XXVIII     Mono(diethanolamine) salt of N-phosphonomethyl-                               glycine                                                            XXIX       Mono(triethylamine) salt of N-phosphonomethylglycine               XXX        Mono(pyridine) salt of N-phosphonomethylglycine                    XXXI       Mono(aniline) salt of N-phosphonomethylglycine                     XXXII      Bis(N-phosphonomethylglycine) hydrochloride hydrate                __________________________________________________________________________

The compositions of this invention are extremely useful in minimumtillage methods of crop culture. Thus, for example, in those instanceswhere it is desirable to plant a sodded or otherwise vegetated acreagewith corn or the like without plowing or otherwise mechanicallypreparing a seed bed, the crop seed can be drill planted in combinationwith a prior or subsequent application of a composition of thisinvention to kill undesired growing vegetation provided that thecomposition is applied before the emergence of the crop plant.

The compositions of this invention are also useful in sod (turf,alfalfa, pasture, etc.) renovation or conversion procedures. Thus, forexample, in situations where a sod or parts thereof has become overgrownwith undesirable plant species, the plants in said area can be sprayedwith a phytotoxic composition of this invention to control all growingplants and from about 2 to 24 hours later depending upon weatherconditions etc., the desired species can be seeded into the dyingvegetation. Where a seed bed is to be prepared about 2 to 3 weeks shouldelapse between treatment and seed bed preparation, in order to providesufficient time for the composition to be assimilated by all parts ofthe undesired plants. In an alternate method of sod renovation, the areacan be seeded and immediately sprayed with a composition of thisinvention. In either method, the seeds fall among the vegetation and asthe sprayed plants wither and die, they act as a mulch and moistureretaining layer in which the seeds can germinate. This method isparticularly useful in the spot renovation of lawns or golf greens orfairways since the herbicidal effect of the compositions of thisinvention is greatly decreased or totally inactivated by contact withsoil. Thus, seeds which are in the soil can germinate and grow withoutany apparent effects from the spraying of the unwanted plants prior tothe time that the seed actually germinates.

The compositions of this invention provide a wide spectrum of weedcontrol and are also extremely useful as general herbicides as well asin controlling unwanted plants in orchards, tree farms, and variouscrops. For example, it has been found that by directing a spray of thecompositions of this invention at the unwanted plants while essentiallypreventing such spray from contacting the leaves of trees, that suchunwanted plants are controlled while there is no apparent injury to thetrees. In such directed spraying, the spray can fall on the woodyportion of the fruit tree or other tree without any apparent effect.Thus, the directed spray method of control is useful with crops such asplantation crops, i.e. rubber, coffee, bananas, tea, etc. and inorchards such as citrus fruits, apples, peaches, pears, nuts, olive, invineyards and in bramble crops and in nursery crops to control theundesired plants; and in crops such as cotton, soybeans, sugarcane andthe like.

The compositions of this invention are also useful for control of weedsbetween cropping seasons, for the renovation of stale seed beds and thelike.

In applying the compositions of this invention to the plants which it isdesired to control, it has been found to be desirable that the plant beemerged from the ground and even more desirable, that the plant be atleast at the 2 leaf stage for maximum effect. It has been found thatwhen the plants to be controlled have a portion of their growth abovethe ground or water, and the above-ground or above-water portion of theplant contacted with the herbicidal compositions of this invention atappropriate rates, the herbicide is translocated to kill such plantparts which are below the ground or water surface.

One can obtain limited selectivity in crops such as cotton, soybeans,sugar cane and like crops by directing the spraying of a composition ofthis invention at a selected concentration on vegetation around the baseof such plants with minimal spray contact with the leafy portions ofsuch crop plants. The directed spraying can be done with or without aprotective device to prevent contact of the spray with the leaves ofsuch crop plants.

A non-exhaustive list of some of the plant species which are controlledby the compositions of this invention, in addition to those shown inTable I, are set forth below:

    ______________________________________                                        Medicago sativa                                                                              Poa annua                                                      Lolium multiflorum                                                                           Hordeum vulgare                                                Hordeum murinum                                                                              Galium aparine                                                 Alopecurus myosuroides                                                                       Bracharia platyphylla                                          Agrostis tenuis                                                                              Plantago lanceolata                                            Phaseolus vulgaris var.                                                                      Mollugo verticillata                                           humilies                                                                      Daucus carota var. sativa                                                                    Portulaca oleracea                                             Stellaria media                                                                              Zea mays                                                       Agrostemma githago                                                                           Spergula arvensis                                              Gossypium hirsutum                                                                           Saponaria vaccaria                                             Agropyron cristatum                                                                          Cucumis sativus                                                Rumex crispus  Eriochloa gracilis                                             Paspalum dilatatum                                                                           Camelina microcarpa                                            Amsinckia intermedia                                                                         Linum usitatissimum                                            Setaria faberil                                                                              Ambrosia trifida                                               Setaria viridis                                                                              Lithospermum officinale                                        Secale cereale Sisymbrium officinale                                          Lamium amplexicaule                                                                          Brassica juncea                                                Datura stramonium                                                                            Avena sativa                                                   Arachis hypogaea                                                                             Pisum sativum                                                  Solanum tuberosum                                                                            Sida spinosa                                                   Cyperus rotundus                                                                             Polypogon monspeliensis                                        Raphanus sativus                                                                             Ambrosia artemisiifolia                                        Rottboellia exaltata                                                                         Brassica napus                                                 Beta vulgaris  Oryza sativa                                                   Amaranthus retroflexus                                                                       Poa trivialis                                                  Cenchrus pauciflorus                                                                         Rumex acetosella                                               Cassia obtusifolia                                                                           Andropogon saccharoides                                        Zea mays var. saccharata                                                                     Fagopyrum tataricum                                            Lycopersicon esculentum                                                                      Citrullus vulgaris                                             Sorghum bicolor                                                                               Brassica kaber var. pinnatifida                               Avena fatua    Erigeron canadensis                                            Plantago lanceolata                                                                          Trifolium pratense -Dactylis glomerata Daucus carota           Solanum carolinense                                                                          Solanum elaegnifolium                                          Franseria tomentosa                                                                          Poa pratensis                                                  Festuca arundinaceae                                                                         Festuca rubra                                                  Agrostis spp   Cynodon dactylon                                               Panicum dichotomiflorum                                                                      Commelina diffusa or communis                                  Pennisetum clandestinum                                                                      Paspalum spp                                                   Mikania cordata                                                                              Ottochloa nodosa                                               Imperata cylindrica                                                                          Axonopus compressus                                            Scleria bancara                                                                              Commellina nudiflora                                           Eleucine indica                                                               ______________________________________                                    

The phytotoxicant compositions, including concentrates which requiredilution prior to application to the plants, of this invention containat least one active ingredient and an adjuvant in liquid or solid form.The compositions are prepared by admixing the active ingredient with anadjuvant including diluents, extenders, carriers and conditioning agentsto provide compositions in the form of finely-divided particulatesolids, pellets, solutions, dispersions or emulsions. Thus the activeingredient can be used with an adjuvant such as a finely-divided solid,a liquid of organic origin, water, a wetting agent, a dispersing agent,an emulsifying agent or any suitable combination of these. From theviewpoint of economy and convenience, water is the preferred diluent,particularly with the highly water-soluble glycine salts such as thealkali metal salts and amine and ammonium salts. With these derivatives,solutions containing as high as five pounds or more of active materialsper gallon can be readily prepared.

The phytotoxicant compositions of this invention, particularly liquidsand soluble powders, preferably contain as a conditioning agent one ormore surface-active agents in amounts sufficient to render a givencomposition readily dispersible in water or in oil. The incorporation ofa surface-active agent into the compositions greatly enhances theirefficacy. By the term "surface-active agent"it is understood thatwetting agents, dispersing agents, suspending agents and emulsifyingagents are included therein. Anionic, cationic and non-ionic agents canbe used with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chainacid esters of sodium isothionate, esters of sodium sulfosuccinate,sulfated or sulfonated fatty acid esters petroleum sulfonates,sulfonated vegetable oils, ditertiary acetylenic glycols,polyoxyethylene derivatives of alkylphenols (particularly isooctylphenoland nonylphenol) and polyoxyethylene derivatives of the mono-higherfatty acid esters of hexitol anhydrides (e.g. sorbitan). Preferreddispersants are methyl cellulose, polyvinyl alcohol, sodium ligninsulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate and sodiumN-methyl-N-(long chain acid) laurates.

Water-dispersible powder compositions can be made containing one or moreactive ingredients, an inert solid extender and one or more wetting anddispersing agents. The inert solid extenders are usually of mineralorigin such as the natural clays, diatomaceous earth and syntheticminerals derived from silica and the like. Examples of such extendersinclude kaolinites, attapulgite clay and synthetic magnesium silicate.The water-dispersible powder of this invention usually contain fromabout 5 to about 95 parts by weight of active ingredient, from about0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 partsby weight of dispersant and from 4.5 to about 94.5 parts by weight ofinert solid extender, all parts being by weight of the totalcomposition. Where required, from about 0.1 to 2.0 parts by weight ofthe solid inert extender can be replaced by a corrosion inhibitor oranti-foaming agent or both.

Aqueous suspensions can be prepared by mixing together and grinding anaqueous slurry of water-insoluble active ingredient in the presence ofdispersing agents to obtain a concentrated slurry of very finely-dividedparticles. The resulting concentrated aqueous suspension ischaracterized by its extremely small particle size, so that when dilutedand sprayed, coverage is very uniform.

Emulsifiable oils are usually solutions of active ingredient inwater-immiscible or partially water-immiscible solvents together with asurface active agent. Suitable solvents for the active ingredient ofthis invention include hydrocarbons and water-immiscible ethers, estersor ketones. The emulsifiable oil compositions generally contain fromabout 5 to 95 parts active ingredient, about 1 to 50 parts surfaceactive agent and about 4 to 94 parts solvent, all parts being by weightbased on the total weight of emulsifiable oil.

Although compositions of this invention can also contain otheradditaments, for example fertilizers, phytotoxicants and plant growthregulants, pesticides and the like used as adjuvants or in combinationwith any of the above-described adjuvants, it is preferred to employ thecompositions of this invention alone with sequential treatments with theother phytotoxicants, fertilizers and the like for maximum effect. Forexample, the field could be sprayed with a composition of this inventioneither before or after being treated with fertilizers, otherphytotoxicants and the like. The compositions of this invention can alsobe admixed with the other materials, e.g. fertilizers, otherphytotoxicants, etc., and applied in a single application. Chemicalsuseful in combination with the active ingredients of this inventioneither simultaneously or sequentially include for example triazines,ureas, carbamates, acetamides, acetanilides, uracils, acetic acids,phenols, thiolcarbamates, triazoles, benzoic acids, nitriles and thelike such as:

3-amino-2,5-dichlorobenzoic acid

3-amino-1,2,4-triazole

2-methoxy-4-ethylamino-6-isopropylamino-s-triazine

2-chloro-4-ethylamino-6-isopropylamino-s-triazine

2-chloro-N,N-diallylacetamide

2-chloroallyl diethyldithiocarbamate

N'-(4-chlorophenoxyl phenyl-N,N-dimethylurea

1,1'-dimethyl-4,4'-bipyridinium dichloride

isopropyl m-(3-chlorophenyl)carbamate

2,2-dichloropropionic acid

S-2,3-dichloroallyl N,N-diisopropylthiolcarbamate

2-methoxy-3,6-dichlorobenzoic acid

2,6-dichlorobenzonitrile

N,n-dimethyl-2,2-diphenylacetamide

6,7-dihydrodipyrido(1,2-a:2',1'-c)-pyrazidiinium salt

3-(3,4-dichlorophenyl)-1,1-dimethylurea

4,6-dinitro-o-sec-butylphenol

2-methyl-4,6-dinitrophenol

ethyl N,N-dipropylthiolcarbamate

2,3,6-trichlorophenylacetic acid

5-bromo-3-isopropyl-6-methyluracil

3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea

2-methyl-4-chlorophenoxyacetic acid

3-(p-chlorophenyl)-1,1-dimethylurea

1-butyl-3-(3,4-dichlorophenyl)-1-methylurea

N-1-naphthylphthalamic acid

1,1'-dimethyl-4,4'-bipyridinium salt

2-chloro-4,6-bis(isopropylamino)-s-triazine

2-chloro-4,6-bis(ethylamino)-s-triazine

2,4-dichlorophenyl-4-nitrophenyl ether

alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine

S-propyl dipropylthiolcarbamate

2,4-dichlorophenoxyacetic acid

N-isopropyl-2-chloroacetanilide

2',6'-diethyl-N-methoxymethyl-2-chloroacetanilide

monosodium acid methanearsonate

disodium methanecarsonate

N-(1,1-dimethylpropynyl)-3,5-dichlorobenzamide

Fertilizers useful in combination with the active ingredients includefor example ammonium nitrate, urea, potash, and superphosphate.

When operating in accordance with the present invention, effectiveamounts of the glycines are applied to above ground portions of plants.The application of liquid and particulate solid herbicidal compositionsto above ground portions of plants can be carried out by conventionalmethods, e.g. power dusters, boom and hand sprayers and spray dusters.The compositions can also be applied from airplanes as a dust or a spraybecause of their effectiveness at low dosages. The application ofherbicidal compositions to aquatic plants is usually carried out byspraying the compositions on the aquatic plants in the area wherecontrol of the aquatic plants is desired.

The application of an effective amount of the compounds of thisinvention to the plant is essential and critical for the practice of thepresent invention. The exact amount of active ingredient to be employedis dependent upon the response desired in the plant as well as suchother factors as the plant species and stage of development thereof, andthe amount of rainfall as well as the specific glycine employed. Infoliar treatment for the control of vegetative growth, the activeingredients are applied in amounts from about 0.01 to about 20 or morepounds per acre. In applications for the control of aquatic plants, theactive ingredients are applied in amounts of from about 0.01 parts permillion to about 1000 parts per million, based on the aquatic medium. Aneffective amount for phytotoxic or herbicidal control is that amountnecessary for overall or selective control, i.e. a phytotoxic orherbicidal amount. It is believed that one skilled in the art canreadily determine from the teachings of this specification, includingexamples, the approximate application rate.

The compositions of this invention are also useful as harvesting aids inmany crops. Thus, for example, the crop could be sprayed with thecompositions of this invention to reduce the bulk of unwanted materialand make the harvesting of the crops easier. Such crops are for example,peanuts, soybeans, and root crops such as potatoes, sugar beets, redbeets, and the like.

Although the invention is described with respect to specificmodifications, the details thereof are not to be construed aslimitations except to the extent indicated in the following claims.

What is claimed is:
 1. A phytotoxic composition comprising an inertadjuvant and an effective amount of a compound of the formula ##EQU1##wherein R is --OR³ wherein R³ is selected from the group consisting ofmonovalent hydrocarbon groups, monovalent hydrocarbon-oxyhydrocarbongroups each containing from 1 to 18 carbon atoms, halogenated monovalenthydrocarbon groups, halogenated monovalent hydrocarbonoxyhydrocarbongroups each containing from 1 to 18 carbon atoms and from 1 to 3halogens, ##EQU2## groups wherein n is from 1 to 4 and R⁴ and R⁵ areindependently selected from the group consisting of hydrogen, alkyl andhydroxyalkyl having 1 through 4 carbon atoms, alkenyl having 2 through 4carbon atoms, R¹ and R² are each independently selected from the groupconsisting of --OH; --OR³ wherein R³ is as above defined and --OR⁶wherein R⁶ is a salt-forming cation selected from the group consistingof cations of alkali metals, alkaline earth metals, copper, zinc,manganese, nickel, ammonium, organic ammonium, provided that when theorganic group is aryl the ammonium salt is a primary amine salt, andmixtures of such salts, provided that no more than two of R, R¹ or R²can be --OR³.
 2. A composition in accordance with claim 1 wherein R is--OR³ and R³ is an alkyl group containing from 1 through 18 carbonatoms, alkenyl having from 2 through 8 carbon atoms, alkynyl having 2through 8 carbon atoms, haloalkyl, haloalkenyl or haloalkynyl havingfrom 1 through 18 carbon atoms and from 1 through 3 halogens and R¹ andR² are --OH, or --OR⁶.
 3. A composition in accordance with claim 2 inwhich R is --OR³ wherein R³ is alkyl or chloroalkyl.
 4. A composition inaccordance with claim 1 in which the compound ismethyl-N-phosphonomethylglycinate.
 5. A composition in accordance withclaim 1 in which the compound is ethyl-N-phosphonomethylglycinate.
 6. Acomposition in accordance with claim 1 in which the compound ischloroethyl-N-phosphonomethylglycinate.
 7. A method which comprisescontacting a plant with a phytotoxic amount of a compound of the formula##STR3## wherein R is --OR³ wherein R³ is selected from the groupconsisting of monovalent hydrocarbon groups, monovalenthydrocarbon-oxyhydrocarbon groups each containing from 1 to 18 carbonatoms, halogenated monovalent hydrocarbon groups, halogenated monovalenthydrocarbonoxyhydrocarbon groups each containing from 1 to 18 carbonatoms and from 1 to 3 halogens, ##STR4## groups wherein n is from 1 to 4and R⁴ and R⁵ are independently selected from the group consisting ofhydrogen, alkyl and hydroxyalkyl having 1 through 4 carbon atoms,alkenyl having 2 through 4 carbon atoms, R¹ and R² are eachindependently selected from the group consisting of --OH; OR³ wherein R³is as above defined and --OR⁶ wherein R⁶ is a salt-forming cationselected from the group consisting of cations of alkali metals, alkalineearth metals, copper, zinc, manganese, nickel, ammonium, organicammonium, provided that when the organic group is aryl the ammonium saltis a primary amine salt, and mixtures of such salts, provided that nomore than two of R, R¹ or R² can be --OR³.
 8. The process of claim 7wherein R is OR³ and R³ is an alkyl group containing 1 through 18 carbonatoms, alkenyl having 2 through 8 carbon atoms, alkynyl having 2 through8 carbon atoms, haloalkyl, haloalkenyl or haloalkynyl having from 1 to18 carbon atoms and from 1 through 3 halogens and R¹ and R² are --OH or--OR⁶.
 9. The process of claim 8 in which R is OR³ wherein R³ is alkylor chloroalkyl.
 10. The process of claim 7 in which the compound ismethyl-N-phosphonomethyl glycinate.
 11. The process of claim 7 in whichthe compound is ethyl-N-phosphonomethyl glycinate.
 12. The process ofclaim 7 in which the compound is chloroethyl-N-phosphonomethylglycinate.